KR20150087302A - Method for preparing cha-type molecular sieves using colloidal aluminosilicate - Google Patents
Method for preparing cha-type molecular sieves using colloidal aluminosilicate Download PDFInfo
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Abstract
Description
The present invention relates to a process for preparing CHA-type molecular sieves using a colloidal aluminosilicate composition containing one or more structure directing agents suitable for synthesizing CHA-type molecular sieves .
Molecular sieves are a class of commercially important crystalline materials. It has a distinct crystal structure with an ordered pore structure represented by a distinct X-ray diffraction pattern. The crystal structure defines cavities and pores that are characteristic of the different species.
Molecular sieves that have the structure code CHA and are verified by the International Zeolite Associate (IZA) are known. For example, the molecular sieve known as SSZ-13 is a known crystalline CHA material. This is disclosed in U.S. Patent No. 4,544,538 issued to Zones on October 1, 1985. In this patent, the SSZ-13 molecular sieve contains N-alkyl-3-quinuclidinol cations, N, N, N-trialkyl-1-adamantanemonium cations and / or N, N , N-trialkyl-2-exoamino norbornane cations.
United States Patent Application Publication No. 2007-0286798 to Cao et al., Published December 13, 2007, discloses a method for preparing CHA-2 by using various SDAs including N, N, N-trimethyl- Type molecular sieve.
However, SDAs useful for making CHA materials are complex, and typically not available in the amounts needed to produce CHA materials on a commercial scale. There is also a continuing need to minimize the concentration of SDA in the reaction mixture. By doing so, the amount of excess SDA material in the reaction waste stream can be eliminated or reduced to a low concentration, making incineration of the waste stream unnecessary. Thus, it would be desirable to find a way to reduce the amount of SDAs in the synthesis of CHA-type molecular sieves.
It has now been found that when a CHA material is prepared using colloidal aluminosilicates containing at least one cyclic nitrogen-containing cationic structure directing agent, the CHA-type molecular sieve Can be prepared.
SUMMARY OF THE INVENTION
(1) a colloidal aluminosilicate composition containing at least one cyclic nitrogen-containing cation; (2) at least one source of elements selected from group 1 and group 2 of the periodic table; And (3) contacting the hydroxide ion under crystallization conditions.
The present invention also includes a process for preparing a CHA-type molecular sieve by:
(a) (1) a colloidal aluminosilicate composition containing at least one cyclic nitrogen-containing cation; (2) at least one source of elements selected from group 1 and group 2 of the periodic table; (3) a hydroxide ion; And (4) preparing a reaction mixture containing water; And
(b) treating the reaction mixture with crystallization conditions sufficient to form crystals of CHA-type molecular sieves.
If the formed molecular sieve is an intermediate material, in order to achieve the desired molecular sieve, the process of the present invention involves an additional post-crystallization process (e. G. Post-synthesis heteroatom lattice substitution Or acid leaching).
The present invention also provides as-synthesized and anhydrous CHA-type molecular sieves having a composition of the following molar ratios.
here:
(1) M is selected from the group consisting of elements from group 1 and group 2 of the periodic table.
(2) Q is at least one cyclic nitrogen-containing cation.
Figure 1 shows a powder X-ray diffraction (XRD) pattern of a prepared aluminosilicate SSZ-13 molecular sieve, prepared according to Example 4 of the present invention.
Figure 2 shows a powder XRD pattern of a calcined aluminosilicate SSZ-13 molecular sieve, prepared according to Example 4 of the present invention.
3 shows a scanning electron micrograph (SEM) photograph of calcined aluminosilicate SSZ-13 molecular sieve prepared according to Example 4 of the present invention.
Introduction
The term "molecular sieve" includes (a) intermediates produced by direct synthesis or (2) post-crystallization treatment (secondary synthesis) and (b) final or target molecular sieves and zeolites. Secondary synthesis techniques enable the synthesis of the target material from the intermediate material by heteroatom lattice substitution or other techniques. For example, the aluminosilicate can be synthesized from intermediate borosilicate by crystallization of B into Al followed by heteroatom lattice substitution. This technique is described, for example, in C.Y. As described in U.S. Patent No. 6,790,433 issued to Chen and Stacey Zones.
Where permitted, all publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety; To the extent that the above disclosure is not inconsistent with the present invention.
Unless otherwise specified, a description of the genus of an element, material or other component, from which a separate component or mixture of components may be selected, is intended to encompass all possible sub-generic Is intended to include combinations. Also, "include" and variations thereof are intended to be non-limiting, such that the listing of items in the list does not exclude other similar items that may be similarly useful in the materials, compositions, and methods of the present invention.
The term " CHA-type molecular sieve "is described in [ Atlas of Zeolite Framework Types , eds. Ch. All molecular sieves and isotopes thereof, referred to as the International Zeolite Society framework code CHA, as described in Baerlocher, LB McCusker and DH Olson, Elsevier, 6th revised edition, 2007. The Atlas of Zeolite Framework Types classify several differentially named materials as having this same CHA form, including SSZ-13 and SSZ-62.
The CHA-type molecular sieve material prepared according to the process described herein is an amorphous material; A unit cell having a non-CHA structural form (e. G., MFI, MTW, MOR, Beta); And / or other impurities (e. G., Heavy and / or organic hydrocarbons). ≪ / RTI >
The present invention relates to a process for the preparation of a CHA-type amine-silicate compound, which comprises using a colloidal aluminosilicate composition containing a cyclic nitrogen-containing cationic structure-directing agent (SDA) selected from the group consisting of cations represented by structural formulas (1) to (15) The present invention relates to a method of manufacturing itself:
N, N, N-trialkyl-1-adamantammonium cations
N, N, N-trialkyl-2-adamantanammonium cations
3-hydroxy-1-alkyl-1-azoniabicyclo [2.2.2] octane cation
(2S) -N, N, N-trialkylbicyclo [2.2.1] heptane-2-ammonium cation
(2R) -N, N, N-trialkylbicyclo [2.2.1] heptane-2-ammonium cation
N, N-dialkylcyclohexylammonium cations
N, N, N-trialkylcyclohexylammonium cations
N, N, N-trialkyl-2-alkylcyclohexylammonium cations
N, N, N-trialkyl-3-alkylcyclohexylammonium cations
N, N-dialkyl-3,3-dialkylpiperidinium cations
N, N-dialkyl-2-alkylpiperidinium cations
1,3,3,6,6-pentaalkyl-6-azonium-bicyclo [3.2.1] octane cations
2-N, N, N-trialkylammonium-bicyclo [3.2.1] octane cations
9-N, N, N-trialkylammonium-bicyclo [3.2.1] nonane cations
(6,6-dialkylbicyclo [3.1.1] heptan-2-yl) -N, N, N-trialkylmethanammonium cation
Wherein R 1 to R 49 are each independently selected from the group consisting of C 1 -C 3 alkyl groups. In one subembodiment , each of R 1 - R 49 is a methyl group. In another subembodiment, each of R 1 -R 27 and R 29 -R 49 is a methyl group and R 28 is an ethyl group.
Reaction mixture
Generally, CHA-type molecular sieves are prepared by the following steps:
(a) (1) a colloidal aluminosilicate composition containing at least one cyclic nitrogen-containing cation; (2) at least one source of elements selected from group 1 and group 2 of the periodic table; (3) a hydroxide ion; And (4) preparing a reaction mixture containing water; And
(b) treating the reaction mixture with crystallization conditions sufficient to form crystals of CHA-type molecular sieves.
If the formed molecular sieve is an intermediate material, the method of the present invention includes an additional step of synthesizing the target molecular sieve by post-synthesis techniques such as heteroatom lattice substitution and acid refinement.
The composition of the reaction mixture in which the CHA-type molecular sieve is formed is shown in Table 1 as the molar ratio.
[Table 1]
Wherein the compositional parameters M and Q are as described herein above.
Methods for making such colloidal aluminosilicates as well as methods for engaging templates useful for making molecular sieves, as well as colloidal aluminosilicate compositions useful in the processes described herein, U.S. Patent Application Publication No. 2007-0104643 to Brian Holland.
As described hereinabove, for each embodiment described herein, the reaction mixture may be formed using at least one source of elements selected from group 1 and group 2 of the periodic table (referred to herein as M) . In one subembodiment, the reaction mixture is formed using a source of an element from group 1 of the periodic table. In another subembodiment, the reaction mixture is formed using a source of sodium (Na). Any M-containing compound that is not detrimental to the crystallization process is suitable. The sources for these Group 1 and Group 2 elements include their oxides, hydroxides, nitrates, sulfates, halides, oxalates, citrates and acetates.
The SDA cation is typically associated with an anion (X < - >), which may be any anion that is not detrimental to the formation of the zeolite. Representative anions include elements from group 17 of the periodic table (e.g., fluoride, chloride, bromide, and iodide), hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate, and the like.
The reaction mixture may be prepared in a batch or continuous manner. The crystal size, shape and crystallization time of the molecular sieves described herein may vary depending on the nature of the reaction mixture and the crystallization conditions.
Crystallization and After synthesis process
In practice, the molecular sieve is prepared by the following steps:
(a) preparing a reaction mixture as described herein above; And
(b) maintaining the reaction mixture under crystallization conditions sufficient to form molecular sieves. (Harry Robson, Verified Syntheses of Zeolitic Materials , 2nd revised edition, Elsevier, Amsterdam (2001)).
The reaction mixture is maintained at an elevated temperature until the molecular sieve is formed. Hydrothermal crystallization is generally carried out under pressure and generally in an autoclave such that the reaction mixture is maintained at a temperature between 130 ° C and 200 ° C for a period of one to six days with autogenous pressure ).
The reaction mixture may be gently stirred or stirred during the crystallization step. It will be understood by those skilled in the art that the molecular sieves described herein may contain impurities such as amorphous materials, unit cells having a structure that is incompatible with the molecular sieve, and / or other impurities (e.g., organic hydrocarbons) .
During the hydrothermal crystallization step, the molecular sieve crystals may be spontaneously nucleated from the reaction mixture. The use of the molecular sieve crystal as a seed material is advantageous in reducing the time required to complete the crystallization to occur. In addition, seeding can cause increased impurities of the resulting product by promoting nucleation and / or molecular sieve formation over any undesirable phase. When used as a seed, the seed crystal is added in an amount of 1 wt% to 10 wt% of the source relative to the composition parameter T used in the reaction mixture.
Once the molecular sieve crystals are formed, the solid product is separated from the reaction mixture by standard mechanical separation techniques such as filtration. The crystals are washed with water and then dried to obtain a molecular sieve crystal in a synthesized state. The drying step can be carried out under atmospheric pressure or under vacuum.
The molecular sieve can be used in the synthesized state, but will typically be thermally treated (calcined). The term " as-stannedized "refers to the molecular sieve after crystallization and before removal of SDA. SDA is sufficient to remove SDA from the molecular sieve by heat treatment (e.g., calcination), preferably in an oxidizing atmosphere (e.g., air, a gas having an oxygen partial pressure greater than 0 kPa) It can be removed at a temperature that can be easily judged. As described in US Pat. No. 6,960,327 to Navrotsky and Parikh, published on Nov. 1, 2005, SDA is also used in photolysis techniques (e.g., under conditions sufficient to selectively remove organic compounds from molecular sieves , Exposing the SDA-containing molecular sieve product to light or electromagnetic radiation having a wavelength shorter than visible light).
The molecular sieve may then be calcined in steam, air or an inert gas at a temperature in the range of from about 200 DEG C to about 800 DEG C for a period of time ranging from 1 to 48 hours or more. Generally, it is desirable to remove the extra-framework cation (e. G., H + ) by ion-exchange or other known methods and replace it with hydrogen, ammonium or any desired metal- desirable.
If the formed molecular sieve is an intermediate material, the desired molecular sieve can be achieved using post-synthesis techniques such as heteroatom lattice displacement techniques. The target molecular sieve (e.g., silicate SSZ-13) can also be achieved by removing heteroatoms from the lattice by well-known techniques such as acid refinement.
The molecular sieve produced from the process of the present invention can be formed into a wide variety of physical shapes. Generally, the molecular sieve may be in the form of a powder, granule, or extrudate having a particle size sufficient to pass through a molded product, such as a 2-mesh screen, and may be applied on a 400-Tyler screen Can be retained. When the catalyst is formed by extrusion, for example with an organic binder, the molecular sieve can be extruded prior to drying, or it can be extruded after being dried or partially dried.
The molecular sieve can be composite with other materials resistant to the temperature and other conditions used in the organic conversion process. Such matrix materials include inorganic and organic materials such as clays, silicas and metal oxides, as well as active and inactive materials and synthetic or naturally occurring zeolites. Examples of such materials and how they can be used are described in U.S. Pat. U.S. Patent No. 4,910,006 issued to Nakagawa on May 31, 1994, and U.S. Patent No. 5,316,753 issued to Nakagawa on May 31,
Characterization of molecular sieves
The CHA molecular sieves prepared by the process of the present invention have a composition (as molar ratio) of synthesized state and anhydrous state as described in Table 2, wherein the compositional parameters M and Q are as described hereinabove:
[Table 2]
The CHA molecular sieve synthesized by the method of the present invention is characterized by an X-ray diffraction pattern. The X-ray diffraction pattern lines in Table 3 are representative of the synthesized CHA molecular sieve prepared according to the present invention. Small deformation of the diffraction pattern can be attributed to a change in the molar ratio of the framework species of a particular sample due to a change in lattice constant. In addition, sufficiently small crystals will affect the shape and intensity of the peaks, resulting in significantly broadening of the peaks. Small deformation of the diffraction pattern can also be attributed to deformation of the organic compound used in the production and also from deformation of the Si / Al molar ratio from sample to sample. Calcination can also cause a small shift in the X-ray diffraction pattern. Despite these small changes, the basic crystal lattice structure remains unchanged.
[Table 3]
Synthesized CHA - Characteristic peaks for the molecular sieve
(a) ± 0.20
(b) the provided X-ray diffraction is based on a relative intensity scale, wherein the strongest line of the X-ray pattern is assigned a value of 100; W (weak) is less than 20; M (intermediate) is 20 to 40; S (strong) is 40 to 60; VS (very strong) is greater than 60.
The X-ray crystallographic pattern line in Table 4 is representative of the calcined CHA-type zeolite prepared according to the present invention.
[Table 4]
Calcined CHA - Characteristic peaks for the molecular sieve
(a) ± 0.20
(b) the provided X-ray diffraction is based on a relative intensity scale, wherein the strongest line of the X-ray pattern is assigned a value of 100; W (weak) is less than 20; M (intermediate) is 20 to 40; S (strong) is 40 to 60; VS (very strong) is greater than 60.
The powder X-ray diffraction patterns disclosed herein were collected by standard techniques. The radiation was CuK-alpha radiation. The peak height and position as a function of 2 [theta], where [theta] is the Bragg angle, was read from the relative intensities of the peaks and the interplanar spacing d in Armstrong units corresponding to the recorded line could be calculated have.
Example
The following examples illustrate the invention, but are not intended to be limiting thereof.
Example One
SSZ -13 Not seeded. Non-synthetic SDA / SiO 2 = 0.04)
A 23 cc Teflon liner was prepared by mixing 8.05 g of colloidal aluminosilicate (TX-15595, supplied by Nalco Company) containing N, N, N-trimethyl-1-adamantanammonium hydroxide as SDA, (SDA / SiO 2 = 0.04) , was filled with the deionized water of 3.75 g 1N KOH solution, and 1.23 g. The mixture was thoroughly mixed. The resulting gel was finished, sealed in a stainless steel autoclave, heated to 170 DEG C with rotation at about 43 rpm and monitoring crystallization progress every 3-4 days by SEM and pH. The crystallization was completed after 7 days of heating. The crystallization product was recovered by filtration and then thoroughly washed with deionized water. The product was dried overnight in air and then dried in an oven at 115 DEG C to provide 1.62 g of SSZ-13 (> 98% yield based on 19.4% solids in Nalco colloidal aluminosilicate).
Example 2
SSZ -13 Not seeded. Non-synthetic SDA / SiO 2 = 0.08)
A 23 cc Teflon liner was prepared by mixing 8.05 g of colloidal aluminosilicate (TX-15595, supplied by Nalco Company) containing N, N, N-trimethyl-1-adamantanammonium hydroxide as SDA, (SDA / SiO 2 = 0.08) , was filled with the deionized water of 3.75 g 1N KOH solution, and 1.23 g. The mixture was thoroughly mixed. The resulting gel was finished, sealed in a stainless steel autoclave, heated to 170 DEG C with rotation at about 43 rpm, and the progress was monitored every 3-4 days by pH and SEM analysis. Crystallization was completed after 7 days.
The crystallization product was recovered by filtration and then thoroughly washed with deionized water. The product was dried overnight in air and then dried in an oven at 115 DEG C to provide 1.64 g of SSZ-13 (> 98% yield based on 19.6% solids in colloidal aluminosilicate).
Example 3
SSZ -13 Seeded synthesis( SDA / SiO 2 = 0.04)
The cationic N, N, N- trimethyl-1-adamantyl colloidal aluminosilicate composition of 8.14 g containing ammonium agent (TX-15595, supplied by Nalco Company) (SDA / SiO 2 = 0.04) as SDA 2.33 g of water and 2.5 g of 1N KOH solution in a Teflon cup. To the mixture, 0.05 g of chabazite seed crystals were added. The mixture was manually stirred using a spatula until a uniform gel was formed. The final molar composition of the gel is as follows:
25 SiO 2 : 0.71 Al 2 O 3 : 625 H 2 O: 1 SDA-OH: 2.5 KOH
At this point, the Teflon cup was sealed and sealed in a stainless steel autoclave. The reaction was heated at 170 占 폚 while rotating at 43 rpm for 4 days. Upon crystallization, the gel was recovered from the autoclave, filtered and washed with deionized water. The reaction gave 1.62 g of SSZ-13.
CHN combustion analysis of the as-produced product showed a total organic mass of 10.94 wt% in the pore (8.23% carbon, 0.78% nitrogen, and 1.93% hydrogen), which contained 10.94% N, N, N-trimethyl- Indicates that adamantammonium cation is present in the product molecular sieve.
Example 4
SSZ -13 Seeded synthesis( SDA / SiO 2 = 0.08)
A 23 cc Teflon liner was prepared by mixing 8.05 g of colloidal aluminosilicate (TX-15595, supplied by Nalco Company) containing N, N, N-trimethyl-1-adamantanammonium hydroxide as SDA, (SDA / SiO 2 = 0.08) , was filled with the deionized water of 3.75 g 1N KOH solution, and 1.23 g. Then 0.05 g SSZ-13 zeolite seed was added. The mixture was thoroughly mixed. The resultant gel was finished, sealed in a stainless steel autoclave, and heated to 170 DEG C with rotation for 4 days. Crystallization was completed after 4 days. The crystallization product was recovered by filtration and then thoroughly washed with deionized water. The product was dried overnight in air and then dried in an oven at 115 캜 to provide 1.5 g of SSZ-13.
The CHN combustion elemental analysis of the sample in this example of the state exhibited a total of 18.93% organic mass in the pores (14.9 wt% C, 2.7 wt% H and 1.33 wt%), Trimethyl-1-adamantanumonium is 18.93% of the total mass of the produced SSZ-13.
The product in the as-prepared state was analyzed by XRD, and the obtained pattern is shown in Fig. Thereafter, the product was calcined, and the calcined product was analyzed by XRD and SEM, and the patterns obtained and the micrographs are shown in Figs. 2 and 3, respectively.
Example 5
SSZ -13 1L synthesis ( SDA / SiO 2 = 0.08)
Example 4 was repeated, but was performed in 1-L scale synthesis. 1-L Teflon liner, 19.6% solids content and having a SiO 2 / Al 2 O 3 ratio of 28.44 N as SDA, N, N- trimethyl-1-adamantyl bit ammonium hydroxide in 348.5 g containing colloidal (TX-15595, supplied by Nalco Company) (SDA / SiO 2 = 0.08). To the colloidal aluminosilicate, 162 g of a 1N aqueous KOH solution and 55 g of deionized water were added. The mixture was thoroughly stirred with Teflon Spatula until a very homogeneous mixture was obtained. Then, 2 g of the prepared SSZ-13 was added as a seed, and the mixture was stirred again for about 5 minutes. The obtained gel was sealed in a 1-L autoclave and heated to 170 DEG C with stirring at 75 rpm for 4 days. The reaction was terminated as confirmed by SEM and XRD analysis. Thereafter, the liner inclusions were filtered, and the resulting cake was thoroughly rinsed with water and again analyzed by SEM and XRD. The reaction gave 68 g of pure CHA (SSZ-13) product.
The material was calcined using the following procedure. A thin layer of the prepared material in the calcination dish was heated in three steps in a muffle furnace under atmospheric pressure of air. The sample was heated from room temperature to 120 ° C at a rate of 1 ° C per minute and was maintained there for 2 hours. Thereafter, the temperature was increased to 540 DEG C at a rate of 1 DEG C per minute, where it was maintained for 5 hours. In the final step, the temperature was increased to 595 DEG C at a rate of 1 DEG C / min, where it was maintained for 5 hours. Thereafter, the muffle furnace was cooled to room temperature. The sample was removed and weighed.
Upon calcination to remove SDA, the sample lost 13.7 wt%. The microporous analysis showed a micropore volume of 0.269 cc / g.
Elements in clearing brace laboratory (Galbraith labs) of the calcined material was analyzed, three showed 20.9 of SAR (SiO 2 / Al 2 O 3) with the ratio by weight% Al and 32.7 wt% Si. In addition, it contained 1.85 wt.% K.
Example 6
SSZ -13 double- template (dual-template) synthesis
3.73 g of a colloidal aluminosilicate composition (TX-15866, by Nalco Company) containing N, N, N-trimethyl-1-adamantanumonium (ADA) and trimethylcyclohexylammonium (TMC) (TMC / Si = 0.16, ADA / Si = 0.04) were mixed in a Teflon cup with 1.33 g water and 0.124 g 45 wt% KOH solution. To the mixture was added 0.007 g of chabazite seed crystals. The mixture was manually stirred using a spatula until a uniform gel was formed. The final molar composition of the gel is as follows:
25 SiO 2 : 0.71 Al 2 O 3 : 625 H 2 O: 5 SDA-OH: 2.5 KOH
At this point, the Teflon cup was sealed and sealed in a stainless steel autoclave. The reaction was heated at 170 占 폚 while rotating at 43 rpm for 4 days. Upon crystallization, the gel was recovered from the autoclave, filtered and washed with deionized water. Analysis of the product by XRD indicated that the product was pure CHA.
Elemental analysis by ICP indicated that the product CHA crystals had SiO 2 / Al 2 O 3 = 32. The micropore volume as determined by nitrogen adsorption of the calcined crystals was 0.29 cc / g.
Example 7
SSZ -13 double- template synthesis
3.95 g of a colloidal aluminosilicate composition (TX-15866, by Nalco Company) containing N, N, N-trimethyl-1-adamantanumonium (ADA) and trimethylcyclohexylammonium (TMC) (TMC / Si = 0.12, ADA / Si = 0.03) were mixed in a Teflon cup with 1.11 grams of water and 0.124 grams of 45 weight percent KOH solution. To the mixture was added 0.007 g of chabazite seed crystals. The mixture was manually stirred using a spatula until a uniform gel was formed. The final molar composition of the gel is as follows:
25 SiO 2 : 0.71 Al 2 O 3 : 625 H 2 O: 3.75 SDA-OH: 2.5 KOH
At this point, the Teflon cup was sealed and sealed in a stainless steel autoclave. The reaction was heated at 170 占 폚 while rotating at 43 rpm for 10 days. Upon crystallization, the gel was recovered from the autoclave, filtered and washed with deionized water. Analysis of the product by XRD indicated that the product was pure CHA.
Claims (9)
(a) providing a composition comprising: (1) a colloidal aluminosilicate composition containing at least one cyclic nitrogen-containing cation; (2) at least one source of elements selected from group 1 and group 2 of the periodic table; (3) a hydroxide ion; And (4) preparing a reaction mixture containing water; And
(b) treating the reaction mixture with crystallization conditions sufficient to form crystals of CHA-type molecular sieves.
Wherein said cyclic nitrogen-containing cations are selected from the group consisting of cations having the following structure and mixtures thereof:
[Wherein R 1 to R 49 are each independently selected from the group consisting of C 1 -C 3 alkyl groups]
Each of R < 4 > -R < 49 > is a methyl group.
Each of R 1 -R 27 and R 29 -R 49 is a methyl group, and R 28 is an ethyl group.
Wherein the at least one cyclic nitrogen-containing cation comprises an N, N, N-trimethyl-1-adamantanammonium (ADA) cation and a trimethylcyclohexylammonium (TMC) cation.
Wherein the molecular sieve is prepared from a reaction mixture comprising as a molar ratio:
(1) M is at least one element selected from Group 1 and Group 2 of the periodic table;
(2) Q is at least one cyclic nitrogen-containing cation;
Wherein the molecular sieve is prepared from a reaction mixture comprising as a molar ratio:
(1) M is at least one element selected from Group 1 and Group 2 of the periodic table;
(2) Q is at least one cyclic nitrogen-containing cation;
Wherein the molecular sieve has a composition of as-made and anhydrous state as a molar ratio,
(1) M is at least one element selected from Group 1 and Group 2 of the periodic table;
(2) Q is at least one cyclic nitrogen-containing cation;
Wherein the molecular sieve has a composition as a molar ratio comprising:
(1) M is at least one element selected from Group 1 and Group 2 of the periodic table;
(2) Q is at least one cyclic nitrogen-containing cation;
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US9493363B2 (en) | 2014-09-26 | 2016-11-15 | Chevron U.S.A. Inc. | Method for making NES framework type zeolites |
US9708192B2 (en) | 2014-11-25 | 2017-07-18 | Chevron U.S.A. Inc. | Method for preparing aluminosilicate molecular sieves having the CHA framework type |
US9452937B2 (en) * | 2014-12-30 | 2016-09-27 | Chevron U.S.A. Inc. | Synthesis of aluminosilicate molecular sieves having the IFR structure type |
CA3003191C (en) | 2015-10-26 | 2024-01-23 | Ecolab Usa Inc. | Highly homogenous zeolite precursors |
JP6953791B2 (en) * | 2016-05-23 | 2021-10-27 | 東ソー株式会社 | CHA-type zeolite and its manufacturing method |
KR102413862B1 (en) * | 2016-09-01 | 2022-06-29 | 셰브런 유.에스.에이.인크. | Synthesis of aluminosilicate zeolite SSZ-26 via inter-zeolite transformation |
JP7125937B2 (en) * | 2016-12-02 | 2022-08-25 | エコラブ ユーエスエイ インク | Polyaluminum salts and their use in the preparation of high purity colloidal alumina-silica composite particles and zeolites |
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WO2023036238A1 (en) * | 2021-09-09 | 2023-03-16 | Basf Corporation | Synthesis of cha zeolitic materials, cha zeolitic materials obtainable therefrom and scr catalysts comprising the same |
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US4160011A (en) * | 1974-12-26 | 1979-07-03 | Texaco Inc. | Crystalline aluminosilicate percursor |
US20050234136A1 (en) * | 2004-04-19 | 2005-10-20 | Holland Brian T | Colloidal compositions and methods of preparing same |
US7754187B2 (en) * | 2005-10-31 | 2010-07-13 | Exxonmobil Chemical Patents Inc. | Synthesis of chabazite-containing molecular sieves and their use in the conversion of oxygenates to olefins |
US20080085563A1 (en) * | 2006-10-10 | 2008-04-10 | Idexx Laboratories, Inc. | Detection of Gadolinium Chelates |
KR101613492B1 (en) * | 2009-04-02 | 2016-04-20 | 셰브런 유.에스.에이.인크. | Method for preparing cha-type molecular sieves using novel structure directing agents |
US8053618B1 (en) * | 2010-06-21 | 2011-11-08 | Uop Llc | UZM-35 zeolitic composition, method of preparation and processes |
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2013
- 2013-11-14 CA CA2892052A patent/CA2892052A1/en not_active Abandoned
- 2013-11-14 CN CN201380067926.6A patent/CN104870369A/en active Pending
- 2013-11-14 EP EP13795964.9A patent/EP2922788A1/en not_active Withdrawn
- 2013-11-14 AU AU2013348274A patent/AU2013348274A1/en not_active Abandoned
- 2013-11-14 KR KR1020157015880A patent/KR20150087302A/en not_active Application Discontinuation
- 2013-11-14 JP JP2015544089A patent/JP2016502490A/en active Pending
- 2013-11-14 US US14/079,926 patent/US20140147378A1/en not_active Abandoned
- 2013-11-14 MX MX2015006512A patent/MX2015006512A/en unknown
- 2013-11-14 WO PCT/US2013/070030 patent/WO2014081607A1/en active Application Filing
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AU2013348274A1 (en) | 2015-06-11 |
US20140147378A1 (en) | 2014-05-29 |
CA2892052A1 (en) | 2014-05-30 |
EP2922788A1 (en) | 2015-09-30 |
JP2016502490A (en) | 2016-01-28 |
CN104870369A (en) | 2015-08-26 |
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